Process for producing foamed resin article

ABSTRACT

The present invention provides a process for producing a foamed resin article, the process comprising: 
     a step (the first step) of impregnating any one crystalline thermoplastic resin or resin composition containing, as an elementary ingredient, a crystalline thermoplastic resin selected from a certain group, under an elevated pressure which is not lower than the critical pressure of a substance with which the selected crystalline thermoplastic resin or resin composition is to be impregnated, with a fluid of the substance, and 
     a step (the second step) of releasing the resin or resin composition impregnated with the substance from the foregoing pressurized condition in a period of less than 10 seconds.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for producing a foamed resinarticle and the like, particularly to a process for producing a foamedresin article having fine cells in a high cell density and the like.

2. Description of the Related Art

In recent years, a supercritical foaming technique wherein a foamedresin article having fine cells in a high cell density is produced byusing an inert substance (carbon dioxide, nitrogen and the like) in asupercritical state has been developed [see, for example, Material &Manufacturing Process, 4 (2), 253-262 (1989) and U.S. Pat. No.5,160,674]. Development of techniques by which higher cell densities canbe achieved is still required, however.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a process forproducing a foamed resin article having fine cells in a higher celldensity, and the like.

The present inventors have studied intensively on a process forproducing a foamed resin article having fine cells in a higher celldensity, and as a result, have found a process for producing a foamedresin article comprising two steps using a specific resin material canattain the above object and have accomplished the present invention.

That is, the present invention provides:

1. a process for producing a foamed resin article, the processcomprising:

a step (the first step) of impregnating any one crystallinethermoplastic resin or resin composition containing, as an elementaryingredient, a crystalline thermoplastic resin selected from ones listedbelow, under an elevated pressure which is not lower than the criticalpressure of a substance with which the selected crystallinethermoplastic resin or resin composition is to be impregnated, with afluid of the substance, and

a step (the second step) of releasing the resin or resin compositionimpregnated with the substance from the foregoing pressurized conditionin a period of less than 10 seconds. (Hereinafter, it may sometimes bereferred to as the process of the present invention.)

(Crystalline Thermoplastic Resin or Resin Composition Containing, as anElementary Ingredient, a Crystalline Thermoplastic Resin)

(a) A polypropylene resin which is a crystalline thermoplastic resin

(b) A resin composition comprising not less than 50% by weight of apolypropylene resin which is a crystalline thermoplastic resin, as anelementary ingredient

(c) A resin composition comprising 60 to 90 parts by weight of acrystalline thermoplastic resin as an elementary ingredient and 10 to 40parts by weight of a non-crystalline thermoplastic resin

(d) A crystalline thermoplastic resin or a crystalline thermoplasticresin composition wherein an endothermic curve obtained by measurementat a rate of heating of 10° C./min using a differential scanningcalorimeter (DSC) has at least one endothermic peak and wherein whentaking the highest peak point among the at least one endothermic peak asA, taking the point appearing on the higher temperature side at whichthe minimum endothermic heat value is given as F, taking the point atwhich a straight line (a base line) which passes through the point F andis parallel to the temperature axis intersects a perpendicular droppedfrom the point A to the temperature axis as B, taking the point whichinternally divides the segment AB in the perpendicular into 9:1 as C,taking the point at which a straight line which passes through the pointC and is parallel to the temperature axis intersects the endothermiccurve at the lowest temperature as D, and taking the point at which theline CD intersects the endothermic curve at the highest temperature asE, a difference in temperature indicated by the length of the segment DEis 20° C. or more.

2. the process for producing a foamed resin article according to theabove 1, wherein the release from the pressurized condition in thesecond step is conducted in a period of 3 seconds or shorter.

3. the process for producing a foamed resin article according to theabove 1, wherein the second step is conducted at a lower temperaturethan a temperature at which the first step is conducted.

4. the process for producing a foamed resin article according to theabove 1, wherein the release from the pressurized condition in thesecond step is conducted at a lower temperature than a melting point ofthe resin or resin composition used.

5. the process for producing a foamed resin article according to theabove 1, wherein the impregnation in the first step is conducted underthe pressurized conditions of at a temperature of 300° C. or lower, in aperiod of 5 hours or shorter and at a pressure of 10 MPa or higher.

6. the process for producing a foamed resin article according to theabove 1, wherein the impregnation in the first step is conducted underthe pressurized conditions of at a temperature in the range of 60 to230° C., in a period of 3 hours or shorter and at a pressure in therange of 10 to 50 MPa.

7. the process for producing a foamed resin article according to theabove 1, wherein the crystalline thermoplastic resin is a polypropyleneresin, which is a crystalline thermoplastic resin. (Hereinafter, it maysometimes be referred to as the process A of the present invention.)

8. the process for producing a foamed resin article according to theabove 1, wherein the resin composition is a resin composition comprisingnot less than 50% by weight of a polypropylene resin which is acrystalline thermoplastic resin, as an elementary ingredient.(Hereinafter, it may sometimes be referred to as the process A′ of thepresent invention.)

9. the process for producing a foamed resin article according to theabove 1, wherein the resin composition is a resin composition comprising60 to 90 parts by weight of a crystalline thermoplastic resin as anelementary ingredient and 10 to 40 parts by weight of a non-crystallinethermoplastic resin. (Hereinafter, it may sometimes be referred to asthe process B of the present invention.)

10. the process for producing a foamed resin article according to theabove 9, wherein the resin composition comprises a crystal phase and anon-crystal phase and the size of the non-crystal phase is 10 to 200 nm.

11. the process for producing a foamed resin article according to theabove 1, wherein the crystalline thermoplastic resin or the resincomposition is a crystalline thermoplastic resin or a crystallinethermoplastic resin composition wherein an endothermic curve obtained bymeasurement at a rate of heating of 10° C./min using a differentialscanning calorimeter (DSC) has at least one endothermic peak and whereinwhen taking the highest peak point among the at least one endothermicpeak as A, taking the point appearing on the higher temperature side atwhich the minimum endothermic heat value is given as F, taking the pointat which a straight line (a base line) which passes through the point Fand is parallel to the temperature axis intersects a perpendiculardropped from the point A to the temperature axis as B, taking the pointwhich internally divides the segment AB in the perpendicular into 9:1 asC, taking the point at which a straight line which passes through thepoint C and is parallel to the temperature axis intersects theendothermic curve at the lowest temperature as D, and taking the pointat which the line CD intersects the endothermic curve at the highesttemperature as E, a difference in temperature indicated by the length ofthe segment DE is 20° C. or more. (Hereinafter, it may sometimes bereferred to as the process C of the present invention.)

12. A foamed resin article produced by the process of the above 1.(Hereinafter, it may sometimes be referred to as the foamed resinarticle of the present invention.)

13. A foamed resin article characterized by being formed of apolypropylene resin which is a crystalline thermoplastic resin, or aresin composition comprising not less than 50% by weight of apolypropylene resin which is a crystalline thermoplastic resin, and byhaving an average cell density of not less than 10¹¹ cells per cubiccentimeter (cm³) of said resin or said resin composition. (Hereinafter,it may sometimes be referred to as the foamed resin article A of thepresent invention.)

14. The foamed resin article according to the above 13, wherein anaverage cell diameter is not greater than 2 μm.

15. A foamed resin article characterized by being formed of a resincomposition comprising 60 to 90 parts by weight of a crystallinethermoplastic resin as an elementary ingredient and 10 to 40 parts byweight of a non-crystalline thermoplastic resin, and by having anaverage cell density of not less than 10¹¹ cells per cubic centimeter(cm³) of said resin or said resin composition. (Hereinafter, it maysometimes be referred to as the foamed resin article B of the presentinvention.)

16. The foamed resin article according to the above 15, wherein thenon-crystalline thermoplastic resin is a polyolefin-based elastomer.

17. The foamed resin article according to the above 16, wherein thepolyolefin-based elastomer is a hydrogenated styrene/butadiene copolymeror a propylene/butene copolymer.

18. A foamed resin article characterized by being formed of acrystalline thermoplastic resin or crystalline thermoplastic resincomposition wherein an endothermic curve obtained by measurement at arate of heating of 10° C./min using a differential scanning calorimeter(DSC) has at least one endothermic peak and wherein when taking thehighest peak point among the at least one endothermic peak as A, takingthe point appearing on the higher temperature side at which the minimumendothermic heat value is given as F, taking the point at which astraight line (a base line) which passes through the point F and isparallel to the temperature axis intersects a perpendicular dropped fromthe point A to the temperature axis as B, taking the point whichinternally divides the segment AB in the perpendicular into 9:1 as C,taking the point at which a straight line which passes through the pointC and is parallel to the temperature axis intersects the endothermiccurve at the lowest temperature as D, and taking the point at which theline CD intersects the endothermic curve at the highest temperature asE, a difference in temperature indicated by the length of the segment DEis 20° C. or more, and by having an average cell diameter of not greaterthan 10 μm and an expansion ratio of not less than twice and not morethan 40 times. (Hereinafter, it may sometimes be referred to as thefoamed resin article C of the present invention.)

According to the foregoing process, a foamed resin article having finecells in a cell density higher than that achieved by foaming resinmaterials other than the above-mentioned crystalline thermoplastic resinor resin composition comprising, as an essential ingredient, acrystalline thermoplastic resin (henceforth, the both may be referred toas “the present resin material”).

Further scope of applicability of the present invention will becomeapparent from the detailed description given hereinafter. However, itshould be understood that the detailed description and specificexamples, while indicating preferred embodiments of the invention, aregiven by way of illustration only, since various changes andmodifications within the spirit and scope of the invention will becomeapparent to those skilled in the art from this detailed description.

Throughout this specification and the claims which follow, unless thecontext requires otherwise, the word “comprise”, and variations such as“comprises” and “comprising”, will be understood to imply the inclusionof a stated integer or step or group of integers or steps but not theexclusion of any other integer or step or group of integer or step.

BRIEF DESCRIPTION OF DRAWINGS

In the accompanying drawings:

FIG. 1 is an electron microscope photograph of a cross section of thefoamed resin article obtained in Example 1;

FIG. 2 is an exemplary endothermic curve by DSC (a schematic drawing) ofa crystalline thermoplastic resin;

FIG. 3 is an endothermic curve by DSC of the linear low densitypolyethylene used in Example 13; and

FIG. 4 is an endothermic curve by DSC of the linear low densitypolyethylene used in Comparative Example 8.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the process of the present invention is first conducted a step (thefirst step) of impregnating the present resin material, under anelevated pressure which is not lower than the critical pressure of asubstance with which the resin material is to be impregnated(henceforth, this substance may be referred to as an impregnatingsubstance), with a fluid of the impregnating substance. Henceforth, thisstep is sometimes referred to as an impregnating step.

The following is an explanation for the cases where the present resinmaterial is:

(a) a polypropylene resin which is a crystalline thermoplastic resin, or

(b) a resin composition comprising not less than 50% by weight of apolypropylene resin which is a crystalline thermoplastic resin, as anelementary ingredient.

The crystalline thermoplastic resin used here may be exemplified bypropylene homopolymers or propylene copolymers containing not less than50% by weight of propylene monomer units. Preferred propylene copolymersinclude binary or ternary copolymers of propylene and ethylene or anα-olefin other than propylene. The α-olefin may be exemplified by linearor branched α-olefins having not less than 4 carbon atoms such as1-butene, 4-methylpentene-1, 1-octene and 1-hexene. Preferred are linearor branched α-olefins having not more than 10 carbon atoms in view ofcopolymerizability with propylene.

From the viewpoint of strength, propylene homopolymers are preferred. Onthe other hand, propylene copolymers are preferred from the viewpointsof flexibility, transparency and the like. In the case of using acopolymer, a content of monomers in the copolymer other than propyleneis preferably not more than 10% by weight for ethylene, not more than30% by weight for other α-olefins. Moreover, from the viewpoint thatfoamed resin articles having high strength and having fine cells can beobtained, mixtures of a propylene homopolymer and a copolymer ofpropylene and ethylene or copolymer of propylene and α-olefin other thanpropylene also are desirable. In the case of using such mixtures, acomposition prepared by separately producing a propylene homopolymer anda copolymer of propylene and ethylene or a copolymer of propylene andα-olefin other than propylene in advance and then kneading them with akneader or the like may be used and also a so-called block copolymerprepared by homopolymerizing propylene and subsequently copolymerizingpropylene and ethylene or propylene and α-olefin other than propylenemay be used. Of course, the block copolymer may be blended with thepropylene homopolymer, the copolymer of propylene and ethylene, thecopolymer of propylene and α-olefin other than propylene or the like.The foregoing polypropylene resins may by used singly or in combinationof two or more of them.

Furthermore, the polypropylene resin may be a polypropylene resin havinglong chain branches introduced by low-level electron beam crosslinking,which is disclosed in Japanese Unexamined Patent Publication No. Sho62-121704, or a polypropylene resin having super high molecular weightcomponents introduced as mentioned later.

Such a polypropylene resin having super high molecular weight componentsintroduce may be exemplified by super high molecular weight-containingpolymers obtained by producing, in the first stage, a crystallinepolypropylene polymer (I) having a limiting viscosity of 5 dl/g or moreby polymerizing monomers mainly containing propylene and successivelyproducing, in the second stage, a crystalline propylene polymer (II)having a limiting viscosity of less than 3 dl/g by polymerizing monomersmainly containing propylene. Among such super high molecularweight-containing polymers, preferred, from the viewpoint of a meltviscosity during foaming, are super high molecular weight-containingpolymers wherein a content of the polymer (I) is not less than 0.05% byweight and less than 35% by weight of the super high molecularweight-containing polymer, a limiting viscosity of the super highmolecular weight-containing polymer is lower than 3 dl/g, and Mw/Mn isless than 10% by weight.

Compositions composed of the aforementioned polypropylene resin and anolefin-based elastomer are desirable as the present resin materialbecause in supercritical foaming as mentioned later using suchcompositions as the present resin material, foamed resin articles havingfine cells in remarkably high cell densities can be obtained.

The foregoing olefin-based elastomers may be exemplified byethylene/α-olefin copolymers, ethylene/propylene/diene copolymers,polybutadiene and hydrogenated products thereof,styrene/isoprene/styrene copolymers, styrene/ethylene/butadiene/styrenecopolymers, styrene/butadiene copolymers,styrene/ethylene/propylene/styrene copolymers andstyrene/butadiene/styrene copolymers. The α-olefin may be exemplified bythe same species as previously mentioned.

In particular, foaming a resin material having a morphology formedtherein wherein non-crystal phases are dispersed in a polypropyleneresin can afford a foamed resin article having extremely fine cells inan extremely high cell density. Therefore an olefin-basedelastomer-containing polypropylene obtained by blending a polypropyleneresin with such an olefin-based elastomer that can be finely dispersedin the polypropylene resin is preferably employed. Specific examples ofsuch useful olefin-based elastomers include styrene/butadiene copolymersand hydrogenated products thereof. In particular, hydrogenatedstyrene/butadiene copolymers containing 10% styrene monomer units arepreferred in the viewpoint of the morphology mentioned above.

When the foamed resin article is formed of an olefin-basedelastomer-containing polypropylene resin composition, an amount of theolefin-based elastomer to be incorporated to 100 parts by weight of thepolypropylene resin preferably is not less than 0.01 parts by weight,and less than 100 parts by weight from the standpoints of heatresistance and oil resistance. Particularly preferred is 1 to 18 partsby weight.

A melt flow rate (MFR) of the resin material used here preferably is notlower than 0.1 from the viewpoints of processability, particularlyextrusion processability. It also preferably is not higher than 50 fromthe viewpoints that a viscosity at which the resin material can stand agas expansion pressure during foaming can be easily maintain, that cellbreakage can be prevented to occur, and that supermicroporous foamedresin articles can be obtained.

The aforementioned resin materials may contain polyethylene resins,examples of which include low density polyethylenes, high densitypolyethylenes, and linear low density polyethylenes. In the case ofincorporating such a polyethylene resin, an amount thereof preferably isnot less than 0.01 parts by weight, particularly not less than 3 partsby weight per 100 parts by weight of the aforementioned resin materialfrom the viewpoint of effects. On the other hand, an amount of thepolyethylene resin preferably is not more than 30 pats by weight,particularly not more than 20 parts by weight, from the viewpoint of itscompatibility with the polypropylene resin. In addition, an MFR of thepolyethylene resin preferably is not lower than 0.1 from the viewpointof its compatibility with the polypropylene resin, and not higher than10 from the viewpoint that cell breakage can be prevented to occur andsupermicroporous foamed resin articles can be obtained.

The resin material used here may be in the form of either powder orpellets, for its preparation may be applied heretofore known techniques.For example, a composition composed of a polypropylene, which is acrystalline thermoplastic resin, and an olefin-based elastomer may beprepared by heretofore known techniques. For example, a method in whichthe both materials are melt kneaded by using a single or twin screwextruder and extruded into pellets may be employed. A Banbury-typekneader may be used for kneading. Incorporation of the foregoingpolyethylene resin may use the same technique as previously mentioned.

The following explanation is for the case where the present resinmaterial is (c) the resin composition comprising 60 to 90 parts byweight of a crystalline thermoplastic resin as an elementary ingredientand 10 to 40 parts by weight of a non-crystalline thermoplastic resin.

The crystalline thermoplastic resin used here may be exemplified bypolyolefin resins (e. g., polyethylene resins and polypropylene resins),polyamide resins, polyethylene terephthalate resins, syndiotacticpolystyrene resin and polyvinyl alcohol resins. Although suchcrystalline thermoplastic resins may be either resins composed only of acrystal phase or resins composed of a crystal phase and a non-crystalphase, the latter are preferable. One species of the crystallinethermoplastic resins may be used or two or more species of them may beused in combination.

Examples of polypropylene resins used here include propylenehomopolymers and propylene copolymers containing not less than 50 mole %of propylene monomer units. Preferred propylene copolymers are binary orternary copolymers of propylene and a copolymerizable monomer such asethylene and/or α-olefin except propylene. The α-olefin may beexemplified by α-olefins having 4 to 10 carbon atoms such as 1-butene,4-methylpentene-1, 1-hexene, 1-octene and 1-decene. A content of therepeating units derived from polymerizable monomers in the foregoingcopolymers is not more than 10% by weight for the cases where thepolymerizable monomer is ethylene and not more than 30% by weight forthe cases of polymerizable monomers other than ethylene.

Moreover, the polypropylene resin may also be either a polypropyleneresin having long chain branches introduced by low-level electron beamcrosslinking, which is disclosed in Japanese Unexamined PatentPublication No. Sho 62-121704, or a polypropylene resin having superhigh molecular weight components introduced. A preferred example of thepolypropylene having super high molecular weight components introducedis one obtained by producing, in the first stage, a crystallinepolypropylene polymer (I) having a limiting viscosity of 5 dl/g or moreby polymerizing monomers mainly containing propylene and successivelyproducing, in the second stage, a crystalline propylene polymer (II)having a limiting viscosity of less than 3 dl/g by polymerizing monomersmainly containing propylene. Among such super high molecularweight-containing polymers, preferred, from the viewpoint of a meltviscosity during foaming, are ones (super high molecularweight-containing polymers) wherein a content of the aforementioned (I)is not less than 0.05% by weight and less than 35% by weight of thesuper high molecular weight-containing polymer, a limiting viscosity ofthe super high molecular weight-containing polymer is lower than 3 dl/g,and Mw/Mn is less than 10.

The non-crystalline thermoplastic resin used here may be, but is notlimited to, thermoplastic elastomers such as polyester elastomers,polyamide elastomers and polyolefin elastomers. Among thenon-crystalline thermoplastic resin mentioned above, the polyesterelastomers are preferably used in combination with crystalline polyesterresins, the polyamide elastomers are preferably used in combination withcrystalline polyamide resins and the polyolefin elastomers arepreferably used in combination with crystalline polyolefin resins. Whenthe aforementioned crystalline thermoplastic resin is composed of acrystal phase and a non-crystal phase, a part of or the whole of theforegoing non-crystalline thermoplastic resin may be dissolved in thenon-crystal of the crystalline thermoplastic resin to expand it. Use ofthe crystalline thermoplastic resin composed of a crystal phase and anon-crystal phase and the non-crystalline thermoplastic resin incombination may adequately adjust the size of the non-crystal phase ofthe crystalline thermoplastic resin.

In particular, when a crystalline polypropylene resin and a polyolefinelastomer are used in combination, examples of preferable polyolefinelastomers include ethylene/α-olefin copolymers, propylene/α-olefincopolymers, ethylene/propylene/diene/methylene copolymers (EPDMR),polybutadienes and their hydrogenated products, styrene/isoprene/styrenecopolymers, styrene/ethylene/butadiene/styrene copolymers,styrene/butadiene copolymers, styrene/ethylene/propylene/styrenecopolymers, and styrene/butadiene/styrene copolymer and theirhydrogenated products. The styrene/butadiene copolymers andpropylene/butene copolymers are more preferable. Hydrogenatedstyrene/butadiene copolymers containing about 10% by weight repeatingunits derived from styrene are especially preferably used.

An amount of the non-crystalline thermoplastic resin in the resincomposition used here is 10 to 40 parts by weight, preferably 10 to 30parts by weight per 100 parts by weight of the sum of thenon-crystalline thermoplastic resin and the aforementioned crystallinethermoplastic resin. When the amount of the non-crystallinethermoplastic resin is less than 10 parts by weight, a satisfactoryeffect on a cell density improvement can not be enjoyed. When it exceeds40 parts by weight, characteristics of the crystalline thermoplasticresin used together tend to deteriorate. For example, in the case of aresin composition composed of a polypropylene resin and anon-crystalline thermoplastic resin, heat resistance and oil resistanceof the polypropylene resin deteriorates when a content of thenon-crystalline thermoplastic resin exceeds 40 parts by weight.

When the aforementioned resin composition contains a polypropyleneresin, a polyethylene resin and a polyolefin-based thermoplasticelastomer, a content of the polyethylene resin is preferably 0.01 to 30%by weight, more preferably 3 to 20% by weight of the total resincomposition. Incorporation of such an amount of the polyethylene resinmay provide a good effect on cell density improvement. A low densitypolyethylene (LDPE), a high density polyethylene (HDPE) and a linear lowdensity polyethylene (LLDPE) are preferably used as the polyethyleneresin. A melt flow rate (MFR) of the polyethylene resin is preferablynot lower than 1 g/10 minutes and not higher than 10 g/10 minutes.

An MFR of the total of the aforementioned resin composition ispreferably in the range of not lower than 0.1 g/10 minutes and nothigher than 50 g/10 minutes. When the MFR is lower than 0.1 g/10minutes, deterioration in extrusion processability becomes pronounced.When the MFR exceeds 50 g/10 minutes, the resin composition can notstand an expansion gas pressure during foaming and causes cell breakage,and there is a tendency of increasing difficulty of obtaining foamedresin articles having uniform fine cells.

The aforementioned resin composition made of the crystallinethermoplastic resin and the non-crystalline thermoplastic resin iscomposed of a crystal phase and a non-crystal phase. When a size of thenon-crystal phase is 10 to 200 nm, a satisfactory effect on cell densityimprovement can be obtained and the size of the non-crystal phase ispreferably 15 to 100 nm. The size of the non-crystal phase used hereinmeans an average determined by the following method. A resin compositionwhich has been cooled and solidified is cut first and a cut section isstained with a coloring matter (for example, RuO₄). The colored part issliced into a thickness of not greater than 1000 Å with a microtomewhile being cooled. The resulting slice is taken its photograph with atransmission microscope (in general, a magnification isapproximately×50,000 to×60,000). In a square viewing field containingabout 50 non-crystal phase sections found in the resulting photograph, adiameter of the largest circle contained in each non-crystal phasesection is measured and the average of the measurements is calculated.This average is defined as the size of the non-crystal phase of theresin composition.

A preparation method of the aforementioned resin composition is notparticularly limited. For example, the resin composition may be preparedby melt kneading the crystalline thermoplastic resin and thenon-crystalline thermoplastic resin by using a single or twin screwextruder, which is generally used for kneading a resin material. Theresulting resin composition may be formed into pellets, a sheet or thelike. The melt kneading may be conducted by using a kneading machinesuch as a Banbury-type mixer.

The following is an explanation for the case where the present resinmaterial is (d) a crystalline thermoplastic resin or a crystallinethermoplastic resin composition wherein an endothermic curve obtained bymeasurement at a rate of heating of 10° C./min using a differentialscanning calorimeter (DSC) has at least one endothermic peak and whereinwhen taking the highest peak point among the at least one endothermicpeak as A, taking the point appearing on the higher temperature side atwhich the minimum endothermic heat value is given as F, taking the pointat which a straight line (a base line) which passes through the point Fand is parallel to the temperature axis intersects a perpendiculardropped from the point A to the temperature axis as B, taking the pointwhich internally divides the segment AB in the perpendicular into 9:1 asC, taking the point at which a straight line which passes through thepoint C and is parallel to the temperature axis intersects theendothermic curve at the lowest temperature as D, and taking the pointat which the line CD intersects the endothermic curve at the highesttemperature as E, a difference in temperature indicated by the length ofthe segment DE is 20° C. or more.

As for the crystalline thermoplastic resin or the crystallinethermoplastic resin composition used here, the difference in temperaturecorresponding to the segment DE is preferably not less than 25° C. andnot more than 100° C., more preferably not less than 30° C. and not morethan 100° C. FIG. 1 shows an exemplary endothermic curve (a schematicdrawing) of a crystalline thermoplastic resin obtained by DSC. Thecrystalline thermoplastic resin used here is not particularly limited inkind as long as its endothermic curve determined by a differentialscanning calorimeter (DSC) meets the aforementioned conditions. Forexample, polyolefin resins (e. g., polyethylene resins and polypropyleneresin), polyamide resins, polyethylene terephthalate resins,syndiotactic polystyrene resins and polyvinyl alcohol resins arementioned. Among these, the polyolefin resins are preferably used. Onespecies of the crystalline thermoplastic resins may be used and also twoor more species of them may be used in combination.

The polyethylene resins used here include low density polyethylenes(LDPE), high density polyethylenes (HDPE), linear low densitypolyethylenes (LLDPE) and ethylene/α-olefin copolymers.

The polypropylene resins used here include propylene homopolymers andpropylene copolymers containing not less than 50 mole % of propylenemonomer units. Preferable propylene copolymers are binary or ternarycopolymers of propylene and a copolymerizable monomer such as ethyleneand/or α-olefin except propylene. The α-olefin may be exemplified byinclude linear or branched α-olefins having not less than 4 carbon atomssuch as 1-butene, 4-methylpentene-1, 1-octene and 1-hexene. From theviewpoint of polymerizability with propylene, linear or branchedα-olefins having not more than 10 carbon atoms.

From strength of foamed resin articles, propylene homopolymers arepreferred. From flexibility or transparency of foamed resin articles,propylene copolymers are preferred. When a propylene copolymer is used,a content of monomer units other than propylene in the copolymer is notmore than 10% by weight for ethylene and not more than 30% by weight forα-olefins. From the viewpoint that foamed resin articles having finecells and good in mechanical strength may be obtained, mixtures ofpropylene homopolymers and propylene/ethylene copolymers orpropylene/α-olefin copolymers are also preferred. In the case of usingsuch a mixture, use of a resin composition prepared by kneading apolypropylene homopolymer and a polypropylene copolymer, which have beenprepared separately, with a kneading machine or the like is permittedand also use of a resin composition prepared by homopolymerizingpropylene and subsequently copolymerizing propylene and acopolymerizable monomer (ethylene or an α-olefin other than propylene)is permitted. Of course, the latter resin composition may be used bybeing mixed with a propylene homopolymer, a propylene/ethylenecopolymer, a propylene/α-olefin copolymer or the like.

Moreover, the polypropylene resin may also be either a polypropyleneresin having long chain branches introduced by low-level electron beamcrosslinking, which is disclosed in Japanese Unexamined PatentPublication No. Sho 62-121704, or a polypropylene resin having superhigh molecular weight components introduced. A preferred example of thepolypropylene having super high molecular weight components introducedis one obtained by producing, in the first stage, a crystallinepolypropylene polymer (I) having a limiting viscosity of 5 dl/g or moreby polymerizing monomers mainly containing propylene and successivelyproducing, in the second stage, a crystalline propylene polymer (II)having a limiting viscosity of less than 3 dl/g by polymerizing monomersmainly containing propylene. Among such super high molecularweight-containing polymers, preferred, from the viewpoint of a meltviscosity during foaming, are ones super high molecularweight-containing polymers wherein a content of the aforementioned (I)is not less than 0.05% by weight and less than 35% by weight of thesuper high molecular weight-containing polymer, a limiting viscosity ofthe super high molecular weight-containing polymer is lower than 3 dl/g,and Mw/Mn is less than 10.

The aforementioned crystalline thermoplastic resin or thermoplasticresin composition preferably has an MFR falling in the range of notlower than 0.1 g/10 minutes and not higher than 50 g/10 minutes. Whenthe MFR is lower than 0.1 g/10 minutes, deterioration in extrusionprocessability becomes pronounced. When the MFR exceeds 50 g/10 minutes,the resin composition can not stand an expansion gas pressure duringfoaming and causes cell breakage, and there is a tendency of increasingdifficulty of obtaining foamed resin articles having uniform fine cells.

A preparation method of the aforementioned crystalline thermoplasticresin or thermoplastic resin composition is not particularly limited.For example, the resin composition may be prepared by melt kneading thepresent resin material by using a single or twin screw extruder, whichis ordinarily used for kneading a resin material. The present resincomposition obtained may be formed into pellets, a sheet or the like.The melt kneading may be conducted by using a kneading machine such as aBanbury type mixer.

In the impregnating step in the process of the present invention, thepresent resin material is impregnated, under an elevated pressure whichis not lower than the critical pressure of a substance (impregnatingsubstance) with which the present resin material is to be impregnated,with a fluid (that is, a liquid or critical fluid) of the substance. Theimpregnating substance preferably used may be substances which are in agas state at ordinary pressure and ordinary temperature, for example,organic compounds such as butane and pentane or inorganic compounds suchas carbon dioxide, air, hydrogen, nitrogen, neon and argon. Theforegoing impregnating substance may be mixtures of two or more species.From the viewpoint of ease to handle, inert substances such as carbondioxide, air, nitrogen, neon and argon are preferred. In particular,carbon dioxide or mixtures of carbon dioxide and other substance(s) arepreferably used from the viewpoints of cost efficiency and safety.

An amount of the aforementioned impregnating substance with which thepresent resin material is impregnated is adequately set in accordancewith kind of the impregnating substance, an expansion ratio and a celldensity of the desired foamed resin article and the like. The lowerlimit thereof is generally an amount sufficient to form fine cells at asufficient expansion ratio. There is no particular upper limit of animpregnating amount, but in general, it is exactly or approximately asaturated solubility of the impregnating substance to the present resinmaterial. The impregnating amount need not achieve the saturatedsolubility. For example, a preferred amount of carbon dioxide with whicha resin composition mainly containing a polyolefin resin is impregnatedfalls preferably in the range of not less than 0.1 part by weight andnot more than 20 parts by weight, more preferably in the range of 0.1 to15 parts by weight, relative to 100 parts by weight of the resincomposition.

A pressure (henceforth, referred to as an impregnation pressure) andtemperature at which the present resin material is impregnated with animpregnating substance, a time required for impregnation and the likevary depending upon a desired impregnating amount. For example, in thecase where a resin composition is impregnated with carbon dioxide, whosecritical pressure is about 7.5 MPa, although an impregnation pressure isrequired only to be at least this critical temperature, it preferably isnot lower than 10 MPa. Moreover, although an upper limit of theimpregnation pressure varies depending upon the ability of equipment andthe like, it generally is about 50 MPa.

A temperature at which the present resin material is impregnated withthe impregnating substance (henceforth, referred to as an impregnationtemperature) is a temperature at which the impregnating substance canbecome a liquid or a critical fluid, and preferably is a temperature notlower than the critical temperature of the impregnating substance. Anupper limit of the impregnation temperature is required only to be atemperature at which the present resin material used does not decompose,and generally is not higher than 300° C. In the case of using carbondioxide, whose critical temperature is about 31° C., the impregnationtemperature preferably is at least this critical temperature, and inparticular, it preferably is not lower than 60° C. from the viewpointsof an infiltrating speed of carbon dioxide to the present resin materialand productivity, and not higher than 230° C. from the viewpoint of asolubility of carbon dioxide to the present resin material.

A time which is spent for impregnating the present resin material withthe impregnating substance (henceforth, referred to as an impregnationtime) varies in accordance with an infiltrating speed of theimpregnating substance to the present resin material and depends uponthe aforementioned impregnation pressure and impregnation temperature.Although continuing the impregnating operation can increase theimpregnating amount up to the saturated solubility, the impregnationtime is generally set to at most a time sufficient for the impregnatingamount of the impregnating substance to achieve the saturatedsolubility, and is generally up to several hours. From the viewpoint ofproductivity, a shorter impregnation time is preferred and there is nonecessity of impregnating the present resin material with theimpregnating substance until its amount achieves its saturatedsolubility. For example, in the case of carbon dioxide in thesupercritical state, an impregnation time is generally from severalminutes to about 5 hours. Preferred is from several minutes to about 3hours from the viewpoint of a balance between productivity and animpregnating amount.

In the process of the present invention, subsequent to theaforementioned impregnation step is carried out a step (the second step)of releasing the present resin material impregnated with theimpregnating substance from the pressurized condition in theaforementioned impregnation step in a period of less than 10 seconds.This step is sometimes referred to as a pressure releasing step in thefollowing explanation.

In the process of the present invention, subsequent to theaforementioned impregnation step is carried out a step (the second step)of releasing the present resin material impregnated with theimpregnating substance from the foregoing pressurized condition in theaforementioned impregnation step in a period of less than 10 seconds(this step is sometimes referred to as a pressure releasing step in thefollowing explanation). The present resin material may further be heatedafter the pressure releasing step. In the pressure releasing step, thereleasing from the pressurized condition is preferably completed in aperiod of less than 10 seconds, more preferably in a period of time asshort as possible. If this operation is conducted slowly, foamed resinarticles having desired cell densities sometimes are not obtained. Ingeneral, the pressure is released from the impregnation pressure toabout ordinary pressure instantaneously. The phrase “to release apressure instantaneously” used herein means to lower a pressure from theimpregnation pressure to about ordinary pressure in a period of time asshort as possible. Depending on a capacity of a container used forimpregnation of the impregnating substance, the thickness of an exhaustpipe and the like, a more preferable period of time for lowering apressure from the impregnation pressure to ordinary pressure may beabout 3 seconds or less.

A sudden release of pressure in the aforementioned pressure releasingstep may be conducted either at a temperature higher than that of theimpregnation step, at a temperature lower than that of the impregnationstep or at the same temperature as that of the impregnation step. Inorder to achieve a finer cell size an a higher cell density, the releaseof pressure is preferably conducted at a lower temperature than that atwhich the impregnation step was conducted. For example, a foamed resinarticle may be obtained by conducting the impregnation step at atemperature not lower than the critical temperature and not higher thanthe melting point of the present resin material; in the pressurereleasing step, suddenly releasing pressure at a temperature higher thanthe temperature of the impregnation temperature, for example atemperature not lower than the melting point of the present resinmaterial to form and grow cell nucleuses; and adequately controlling thegrowth of the cell nucleuses by taking advantage of the drop intemperature caused by the sudden release of pressure. Moreover, a foamedresin article may also be obtained by setting the present resin materialto a temperature not lower than the melting point of the present resinmaterial; in the pressure releasing step, once cooling the present resinmaterial down to a temperature not higher than said melting point;subsequent to this, suddenly releasing pressure to form cell nucleuses;and further growing the cell nucleuses adequately. Furthermore, it isalso permitted to set the temperature at the impregnation step nothigher than the melting temperature of the present resin material andconducting the pressure releasing step at that temperature. In order toachieve a finer cell size and a higher cell density, it is preferable tocarry out the release of pressure at a temperature lower than that ofthe impregnation step.

In order to control cell breakage as much as possible, a temperature ofthe present resin material at the time of pressure releasing ispreferably not higher than the melting point of the present resinmaterial. In order to achieve a finer cell size and a higher celldensity, it preferably is in the range of not lower than (the meltingpoint of the present resin material −100° C.) and not higher than themelting point of the present resin material, more preferably is in therange of not lower than (the melting point of the present resin material−50° C.) and not higher than the melting point of the present resinmaterial. A temperature at which pressure is released is not required tobe constant. In general, the temperature drops with the pressurereleasing. Although there is no necessity of controlling such drop intemperature, it is preferable to control the drop in temperature fromthe viewpoint of controlling a cell density.

Furthermore, in order to control the cell density more adequately, it ispreferable that, in the pressure releasing step, temperatures and timesof both a process of growing cell nucleuses conducted subsequent to aprocess of forming cell nucleuses and a process of stopping the growthof cells are further controlled.

In the aforementioned process of growing cell nucleuses, a temperatureat which the cell nucleuses are grown is preferably controlled to fallwithin the range of not lower than the crystallizing temperature of thepresent resin material and not higher than the melting point of thismaterial in order to control the cell breakage as much as possible. Aperiod of time for growing cell nucleuses is generally 20 seconds to 30seconds though it may be set adequately in accordance with the desiredcell density.

For the purpose of controlling the cell breakage caused by excessivegrowth of cells, it is preferable to control the temperature during theprocess of stopping the growth of cells as well as that during theprocess of growing cell nucleuses. The temperature at which the growthof cells is stopped is preferably not higher than the crystallizingtemperature of the present resin material and it is also preferable thatthe whole foamed resin article is fully cooled until it reaches atemperature not higher than its crystallizing temperature.

Although the above explanation mainly describes embodiments in which theprocess of the present invention is conducted in a batch system, acontinuous system in which the impregnation step and the pressurereleasing step are carried out continuously, for example, by using asingle or multiple screw extruder may be applied for the process of thepresent invention.

Examples of the foamed resin articles of the present invention include:

the foamed resin article A of the present invention which may beproduced by the process A or A′ of the present invention;

the foamed resin article B of the present invention which may beproduced by the process B of the present invention; and

the foamed resin article C of the present invention which may beproduced by the process C of the present invention.

In the case of the foamed resin article A or B, the foamed resin articlehas an average cell density of not less than 10¹¹ cells per cubiccentimeter (cm³). From the viewpoint of a balance among strength, heatresistance and light weight, it preferably has an average cell densityof not less than 10¹² cells/cm³ and an average cell diameter of notgreater than 2 μm.

Moreover, although the foamed resin article comprises not less than 50%by weight of a propylene resin which is a crystalline thermoplasticresin, as an elementary ingredient, whose content is preferably at least70% by weight, more preferably 85% by weight, from the viewpoints ofstrength, heat resistance and the like of a foamed resin article.

In the case of the foamed resin article C, the foamed resin article hasan average cell diameter of not greater 10 μm and an expansion ratio ofnot less than twice and not more than 40 times, but it preferably has anaverage cell diameter ranging 0.01 to 1 μm and an expansion ratio of notless than 10 times and not more than 30 times.

According to the present invention, a foamed resin article having finecells in a higher cell density, which has a high expansion ratio, andwhich is excellent in both light weight property and secondaryworkability. Such a foamed resin article is also excellent in mechanicalstrength, and therefore can be suitably employed, for example, forautomobile parts, trays of containers for food items, buildingmaterials, cushion materials, heat insulating materials and the like.

EXAMPLES

The following examples further explain the present invention, but theinvention is not limited to these examples.

Size of Non-crystal Phase

The present resin material which had been cooled and solidified was cutwith a microtome and a cut section was stained with RuO₄. The stainedpart was sliced into a thickness of not greater than 1000 Å with amicrotome while being cooled. The resulting slice was taken itsphotograph by a transmission electron microscope with a magnification of×60,000. The size of non-crystal phases (an average value) wasdetermined from the resulting photograph.

Average Cell Diameter

A foamed resin article was cooled with liquid nitrogen and thereaftercut with a razor. A section was taken its photograph using a scanningelectron microscope. A magnification of the microscope was adjusted sothat about 50 cells could be seen in a viewing field of the electronmicroscope. From the resulting photograph of the section of the foamedresin article was measured the longest length of each cell in theviewing field, whose average was then calculated. The average of theresulting longest lengths was taken as the average cell diameter (2r).

Average Cell Density

The number (n) of cells per square centimeter (cm²) of the cross sectionof the foamed resin article was calculated from the photograph by anelectron microscope used in the measurement of the average celldiameter. The number of cells (N) per unit volume was calculated byraising the resulting n to the three seconds power. From this number ofcells (N) and the average cell diameter (2r) obtained above wascalculated the number of cells per real unit volume of the present resinarticle constituting the foamed resin article, that is, the average celldensity (unit: cells/cm³ material).

The detail is described below.

The term “the average cell density” has a concept which means the numberof cells present in a portion of a foamed resin article formed of a unitvolume (1 cm³) of a plastic material and is expressed by using the unit,cells/cm³.

An arbitrary section of a foamed resin article is first observed by anSEM (a scanning electron microscope), and from the number of cellsobserved in the viewing field is calculated the number of cells per unitsection (1 cm²), n (cells). The magnification of the SEM is onlyrequired to be a magnification at which cells can be observed clearly,and preferably is a magnification such that approximately 20 to 50 cellscan be seen in a viewing field in general, and generally is from severalhundreds times to about 10,000 times. The above-obtained n to the powerof three seconds corresponds to the number of cells present per unitvolume (1 cm³) of the foamed resin article, N (cells).

On the other hand, for each cell observed in the SEM viewing field usedin the aforementioned measurement of the number of cells, the longestlength is measured and the average thereof, 2r (cm), is calculated,which is defined as the average cell diameter of cells in the foamedresin article. Under the assumption that all of the cells present in thefoamed resin are spheres of radius r (cm), the total volume V₁ (cm³) ofthe cells present in a unit volume (1 cm³) of the foamed resin articleis calculated in accordance with the following formula:

V1=(4πr ³/3)×N

The volume V (cm³) of the plastic material occupying the unit volume ofthe foamed resin article is given by the following formula:

V=1−V ₁

Accordingly, the average cell density (cells/cm³) used in the presentinvention is defined by the following formula:

Average cell density=1/{1/N−4πr ³/3}

Differential Scanning Calorimetry (DSC)

Using the model DSC-7 manufactured by Perkin-Elmer Ltd., an endothermiccurve was recorded by heating about 10 mg of a sample at a rate ofheating of 10° C./min from 30° C. to 200° C., maintaining it at thistemperature for 1 minute, thereafter cooling the sample at a rate of 10°C./min down to 30° C. to solidify it, maintaining it at this temperaturefor 1 minute, and then heating it at a rate of 10° C./min again.

Secondary Workability

A foamed resin sheet 1.5 mm in thickness was vacuum formed into acontainer 15 cm in diameter and 5 cm in height. The appearance of theresulting formed article was evaluated. A ratio of the area wheredefects such as depressions, uneven thickness and the like to the totalsurface area was determined. The higher the volume of this ratio thepoorer the secondary workability. The lower the value the better thesecondary workability.

Examples 1 to 6

Used as a raw resin (a resin material) was an olefin-basedelastomer-containing polypropylene resin composition prepared by meltblending, using a laboplast mill, 90% by weight of polypropylene(polypropylene manufactured by Sumitomo Chemical Co., Ltd., NobleneW101; MFR=8 to 10; propylene homopolymer) and 10% by weight of ahydrogenated styrene/butadiene copolymer rubber (SBR) (1320Pmanufactured by Japan Synthetic Rubber Co., Ltd.; styrene monomer unitcontent=10%; MFR=3.5). The raw resin was press molded into six sheets(thickness=1.5 mm; length=4 cm; width=2 cm) (press conditions:preheating at 230° C. for 3 minutes, pressing for 1 minute, and coolingfor 5 minutes with a pressing plate kept at 30° C.). For every sheet,one sheet was placed in an autoclave which was equipped with a pressuregauge and an exhaust valve and whose temperature had been elevated to apredetermined temperature, and the autoclave was then covered with alid. Carbon dioxide was thereafter pressed into the autoclave with pumpand was forced to be in a supercritical state. The sheet was impregnatedwith the carbon dioxide at an impregnation pressure, at an impregnationtemperature, for an impregnation time given in Table 1. The moment thepressure gauge reached the predetermined pressure was taken as thebeginning of impregnation. The impregnation operation was continuedwhile the impregnation pressure was kept. After the predeterminedimpregnation time had passed, the carbon dioxide was spewed from theautoclave through the exhaust valve to quickly release a pressure insidethe autoclave from the impregnation pressure to ordinary pressure (about0.1 MPa) (a releasing time=2 to 3 seconds).

After the pressure inside the autoclave had become ordinary pressure,the resulting foamed resin article was taken out and its average celldiameter and average cell density were determined. The results are shownin Table 1.

TABLE 1 Impreg- Impreg- Average Average nation Impregnation nation cellcell pressure¹⁾ temperature time diameter density Example (MPa) (° C.)(h) (μm) (cells/cm³) 1 20 135 2 0.25 10¹³ 2 20 145 2 0.5 10¹² 3 20 150 20.75   7 × 10¹¹ 4 26 155 1 2.5   2 × 10¹¹ 5 40  80 1 3 1.1 × 10¹¹ 6 40145 2 0.25 2.2 × 10¹³ ¹⁾Gauge pressure

Examples 7 to 12

90 Parts by weight of polypropylene (Sumitomo Noblene W101 manufacturedby Sumitomo Chemical Co., Ltd.; MFR=8 to 10 g/10 minutes) and 10 partsby weight of a hydrogenated styrene/butadiene copolymer (1320Pmanufactured by JSR Corp.; styrene content=10%; MFR=3.5 g/10 minutes)were melt blended by a twin screw extruder and extruded into a sheet(thickness=1.5 mm; length=4 cm; width=2 cm; size of non-crystalphases=15 nm). This sheet was placed in an autoclave, into which wasthen introduced supercritical carbon dioxide, so that the foregoingsheet was impregnated with the carbon dioxide. The pressure, temperatureand time spent at the impregnation are given in Table 2. After thepredetermined time had passed, the pressure inside the autoclave wasreleased and the resulting foamed resin article was taken out.

TABLE 2 Average Impreg- Impreg- Average cell nation Impregnation nationcell density pressure temperature time diameter (cells/cm³ (MPa) (° C.)(h) (μm) material) Example 1 20 135 2 0.25 10¹³ Example 2 20 145 2 0.510¹² Example 3 20 150 2 0.75   7 × 10¹¹ Example 4 26 155 1 2.5   2 ×10¹¹ Example 5 40  80 1 3 1.1 × 10¹¹ Example 6 40 145 2 0.25 2.2 × 10¹³

Comparative Examples 1 to 5

A sheet (thickness=1.5 mm; length=4 cm; width=2 cm; size of non-crystalphases=9 nm) composed only of polypropylene (Sumitomo Noblene W101manufactured by Sumitomo Chemical Co., Ltd.; MFR=8 to 10 g/10 minutes)was placed in an autoclave, into which was then introduced supercriticalcarbon dioxide, so that the foregoing sheet was impregnated with thecarbon dioxide. The pressure, temperature and time spent at theimpregnation are given in Table 3. After the predetermined time hadpassed, the pressure inside the autoclave was released. In ComparativeExample 5, the sheet was immersed in a 170° C. oil bath for 30 secondsto be foamed after the pressure releasing.

TABLE 3 Average Impreg- Impreg- Average cell nation Impregnation nationcell density pressure temperature time diameter (cells/cm³ (MPa) (° C.)(h) (μm) material) Comparative 20 135 2 — — Example 1 Comparative 20 1652 250 1.2 × 10⁶ Example 2 Comparative 20 155 2  50 2.2 × 10⁷ Example 3Comparative 26 155 1 100   1 × 10⁶ Example 4 Comparative 40  80 1 15 to20 10⁸ Example 5 “—” means that no foam was formed.

Comparative Examples 6, 7

A sheet (thickness=1.5 mm; length=4 cm; width=2 cm; size of non-crystalphases=1000 nm) composed of 90 parts by weight of polypropylene(Sumitomo Noblene W101 manufactured by Sumitomo Chemical Co., Ltd.;MFR=8 to 10 g/10 minutes) and 10 parts by weight of polystyrene (GPPS)was placed in an autoclave, into which was then introduced supercriticalcarbon dioxide, so that the foregoing sheet was impregnated with thecarbon dioxide. The pressure, temperature and time spent at theimpregnation are given in Table 4. After the predetermined time hadpassed, the pressure inside the autoclave was released. After thepressure releasing, the resulting sheet was immersed in a 170° C. oilbath for 30 minutes.

TABLE 4 Average Impreg- Impreg- Average cell nation Impregnation nationcell density pressure temperature time diameter (cells/cm³ (MPa) (° C.)(h) (μm) material) Comparative 40 40 2 10 to 15 10⁷ Example 6Comparative 40 60 2 10 to 15 10⁸ Example 7

Example 13

A sheet (thickness=1.5 mm; length=20 cm; width=20 cm) was prepared bypreheating linear polyethylene (VL200 manufactured by Sumitomo ChemicalCo., Ltd.; MFR=2 g/10 minutes; melting point=109° C.) at 160° C. for 3minutes, thereafter pressing it for 1 minute, and then cooling it for 5minutes with a pressing plate kept at 30° C. The endothermic curve byDSC of the polyethylene used is shown in FIG. 3.

Subsequently, the sheet was placed in an autoclave which was equippedwith a pressure gauge and an exhaust valve and whose temperature hadbeen elevated to a predetermined temperature, and the autoclave was thencovered with a lid. Carbon dioxide was thereafter pressed into theautoclave and was forced to be in a supercritical state. The sheet wasimpregnated with the carbon dioxide at an impregnation pressure of 20MPa, at an impregnation temperature of 90° C., for an impregnation timeof 2 hours. The moment the pressure gauge reached the predeterminedpressure was taken as the beginning of impregnation. The impregnationoperation was continued while the impregnation pressure was kept. Afterthe predetermined impregnation time had passed, the carbon dioxide wasspewed from the autoclave through the exhaust valve to quickly release apressure inside the autoclave until it became ordinary pressure (about0.1 MPa). It took approximately 2 to 3 seconds for releasing pressure.The temperature at pressure releasing was 90° C.

After the pressure inside the autoclave had become ordinary pressure,the resulting foamed resin article was taken out and its average celldiameter and average cell density were determined.

Vacuum forming was carried out using the resulting foamed resin article.The results are shown in Table 6.

Comparative Example 8

A foamed resin sheet was prepared in the same manner as that in Example13 except that a linear low density polyethylene (FZ204-0 manufacturedby Sumitomo Chemical Co., Ltd.; MFR=2 g/10 minutes; melting point=124°C.) was used in stead of the linear low density polyethylene used inExample 13 and that impregnation conditions were set as given in Table5. Vacuum forming was further conducted. The endothermic curve by DSC ofthe polyethylene used is shown in FIG. 3. The evaluation results aregiven in Table 6.

TABLE 5 DSC Impregnation Impregnation Impregnation temperature pressuretemperature time difference (MPa) (° C.) (h) (° C.) Example 13 20 90 275 Comparative 20 110 2 18 Example 8

TABLE 6 Average cell Average cell density Expansion diameter (cells/cm³Secondary ratio (μm) material) workability Example 13 × 10  7.5 10¹⁰0.01 Comparative × 1.5 20 10⁶  0.5 Example 8

What is claimed is:
 1. A process for producing a foamed resin article,the process comprising: a step (the first step) of impregnating any onecrystalline thermoplastic resin or resin composition containing, as anelementary ingredient, a crystalline thermoplastic resin selected fromones listed below, under an elevated pressure which is not lower thanthe critical pressure of a substance with which the selected crystallinethermoplastic resin or resin composition is to be impregnated, with afluid of the substance, and a step (the second step) of releasing theresin or resin composition impregnated with the substance from theforegoing pressurized condition in a period of less than 10 seconds,(Crystalline thermoplastic resin or resin composition containing, as anelementary ingredient, a crystalline thermoplastic resin) (a) Apolypropylene resin which is a crystalline thermoplastic resin (b) Aresin composition comprising not less than 50% by weight of apolypropylene resin which is a crystalline thermoplastic resin, as anelementary ingredient (c) A resin composition comprising 60 to 90 partsby weight of a crystalline thermoplastic resin as an elementaryingredient and 10 to 40 parts by weight of a non-crystallinethermoplastic resin said crystalline thermoplastic resin or acrystalline thermoplastic resin composition wherein said compositioncontains as an elementary ingredient, a crystalline thermoplastic resin,having an endothermic curve obtained by measurement at a rate of heatingof 10° C./min using a differential scanning calorimeter (DSC) has atleast one endothermic peak and wherein when taking the highest peakpoint among the at least one endothermic peak as A, taking the pointappearing on the higher temperature side at which the minimumendothermic heat value is given as F, taking the point at which astraight line (a base line) which passes through the point F and isparallel to the temperature axis intersects a perpendicular dropped fromthe point A to the temperature axis as B, taking the point whichinternally divides the segment AB in the perpendicular into 9:1 as C,taking the point at which a straight line which passes through the pointC and is parallel to the temperature axis intersects the endothermiccurve at the lowest temperature as D, and taking the point at which theline CD intersects the endothermic curve at the highest temperature asE, a difference in temperature indicated by the length of the segment DEis 20° C. or more.
 2. A foamed resin article characterized by beingformed of a crystalline thermoplastic resin or crystalline thermoplasticresin composition wherein an endothermic curve obtained by measurementat a rate of heating of 10° C./min using a differential scanningcalorimeter (DSC) has at least one endothermic peak and wherein whentaking the highest peak point among the at least one endothermic peak asA, taking the point appearing on the higher temperature side at whichthe minimum endothermic heat value is given as F, taking the point atwhich a straight line (a base line) which passes through the point F andis parallel to the temperature axis intersects a perpendicular droppedfrom the point A to the temperature axis as B, taking the point whichinternally divides the segment AB in the perpendicular into 9:1 as C,taking the point at which a straight line which passes through the pointC and is parallel to the temperature axis intersects the endothermiccurve at the lowest temperature as D, and taking the point at which theline CD intersects the endothermic curve at the highest temperature asE, a difference in temperature indicated by the length of the segment DEis 20° C. or more, and by having an average cell diameter of not greaterthan 10 μm and an expansion ratio of not less than twice and not morethan 40 times.